Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
  • C08F220/68—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
  • C08F4/08—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkali metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/287—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene oxide in the alcohol moiety

Definitions

• Lithium hydroxide is a known transesterification catalyst for making methacrylate ester monomers via reaction of methyl methacrylate (MMA) with specialty alcohols (for example, see US 6,048,916, GB 1,094,998, US 5,072,027, US 4,916,255, US 4,672,105, JP 200705591 OA).
• Inhibitors are typically employed in these reactions to keep the monomers from polymerizing during processing. Inhibitors often include, among others, the methyl ether of hydroquinone (MeHQ) and/or phenothiazine (PTZ).
• the catalyst is often removed via filtration procedures that include the addition of either some solid filtration agent (such as diatomaceous earth; in addition to above references, also see JP03109350A) or a hydrocarbon solvent (see JP3106847A) to aid in precipitation and/or removal of the precipitated lithium salts.
• some solid filtration agent such as diatomaceous earth; in addition to above references, also see JP03109350A
• a hydrocarbon solvent see JP3106847A
• the invention provides a transesterification process to form a composition comprising an asymmetrical polyene, the asymmetrical polyene comprising an " ⁇ , ⁇ unsaturated - carbonyl end" and a "C-C double bond end," the process comprising reacting an alkene- or polyene-containing alcohol with an alkyl ester of an alpha, beta unsaturated carboxylic acid in the presence of at least the following components A) through C), to form a solution comprising the asymmetrical polyene:
• the invention is a process to form a composition comprising an asymmetrical polyene, the asymmetrical polyene comprising an " ⁇ , ⁇ unsaturated - carbonyl end" and a "C-C double bond end," the process comprising reacting an alkene- or polyene- containing alcohol with an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in the presence of at least the following components A) through C), to form a solution comprising the asymmetrical polyene:
• An inventive process may comprise a combination of two or more embodiments described herein.
• the transesterification process of the present invention produces an asymmetrical polyene and involves a first step of reacting an alkene- or polyene-containing alcohol with an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid.
• alkene- or polyene-containing alcohol refers to an organic compound comprising at least one C-C double bond and at least one hydroxyl group.
• the alkene- or polyene-containing alcohol comprises an alcohol selected from the group consisting of the following:
• each Z group is independently H or a polyalkylene oxide with the structure:
• R and R' are independently selected from H, CH 3 , or CH3CH2, and n is from 0 to 50, and wherein the dashed line (— ) represents the connecting bond between the alcohol functionality of the alkene- or polyene-containing alcohol with the polyalkylene oxide moiety.
• Peroxides are often present in alkene- or polyene-containing alcohols and their derivatives. These peroxides are undesired because of their propensity to (i) induce unwanted polymer formation from the ⁇ , ⁇ -unsaturated carboxylates present within the compositions disclosed here, and (ii) produce unwanted byproducts, which can impact downstream applications.
• the alkene- or polyene-containing alcohols used in the present transesterification process preferably have a peroxide level less than 50 ppm, or more preferably less than 20 ppm, or most preferably less than 10 ppm, based on the total weight of the alcohol.
• suitable alkene- or polyene-containing alcohols useful in the present transesterification process include, and are not limited to, polypropylene glycol mono- allyl ether and polyethylene glycol mono-allyl ether.
• the alkene- or polyene-containing alcohol is an alkene-containing alcohol.
• the alkene-containing alcohol is preferably polypropylene glycol allyl ether having the structure: wherein n is 1-20, more preferably 1-15, and even more preferably 1-10; R a is selected from H or an alkyl (preferably ethyl or methyl, and more preferably methyl); R is selected from H or an alkyl (preferably ethyl or methyl, and more preferably methyl); and preferably wherein R a and R b are selected from the group consisting of (i) R a and R b are both H, (ii) when R a is methyl, then R b is H, and (iii) when R a is H, then R b is methyl.
• the amount of the alcohol present in the transesterification process described herein is the limiting reactant.
• an alkene- or polyene-containing alcohol may comprise one or more embodiments as described herein. In one embodiment, an alkene- or polyene-containing alcohol may comprise a combination of two or more embodiments as described herein.
• the transesterification process of the present invention produces an asymmetrical polyene and involves a first step of reacting an alkene- or polyene-containing alcohol, as described above, with an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid (or ⁇ , ⁇ unsaturated carboxylic ester).
• alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid refers to an organic compound comprising at least one carbonyl group (CO) and a C-C double bond adjacent to the carbonyl group.
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid selected from the group consisting of the followin :
• Ri is H or CH 3 and each R 2 is, independently, a linear or branched Ci to C 8 alkyl.
• suitable alkyl esters of ⁇ , ⁇ unsaturated carboxylic acids useful in the transesterification process of the present disclosure include, and are not limited to, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl itaconate, ethyl itaconate, and butyl itoconate and combinations thereof,
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is preferably selected from methyl acrylate and methyl methacrylate. In one embodiment, the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is more preferably methyl methacrylate.
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises methyl methacrylate havin the structure (III):
• the amount of alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in the reaction mixture is in stoichiometric excess to the amount of alkene- or polyene-containing alcohol present.
• the mole ratio of alkene or polyene-containing alcohol to alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is from 1 : 1.2 to 1 :20.
• the mole ratio of alkene- or polyene-containing alcohol to alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is from 1 : 1.12 to 1 : 10.
• the mole ratio of alkene- or polyene- containing alcohol to alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is from 1 :2 to 1 :6.5
• the mole ratio of alkene- or polyene-containing alcohol to alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is from 1 :2 to 1 :5.
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises one or more embodiments as described herein. In one embodiment, the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises a combination of two or more embodiments as described herein.
• the process of the invention is a transesterification process comprising reacting an alkene- or polyene-containing alcohol with an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in the presence of at least A) a lithium salt ("component A”); B) a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl-substituted hydroquinone, a substituted alkyl- substituted hydroquinone, and combinations thereof ("component B”); and C) an N-oxyl- containing compound ("component C").
• component A a lithium salt
• component B a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl-substituted hydroquinone, a substituted alkyl- substituted hydroquinon
• the lithium salt (component A) comprises a single lithium salt.
• the lithium salt is a mixture of two or more lithium salts.
• the lithium salt is part of a mixed salt catalyst, such as those known for catalyzing transesterification processes and described in US 2007/028784.
• the lithium salt is selected from the group consisting of lithium salts having the general formula Li n X, wherein n is from 1 to 2 and X is selected from the group consisting of hydroxide, oxide, halide, sulfate, bisulfate, sulfonate, phosphate, phosphonate, perchlorate, nitrate, alkoxide (RO " , wherein R is a straight chain or branched alkyl group having 1 to 8 carbon atoms), phenoxide, carbonate (i.e. C0 3 "2 ), bicarbonate (i.e.
• the lithium salt is selected from the group consisting of lithium salts having the general formula Li n X, wherein n is from 1 to 2 and X is selected from the group consisting of hydroxide, oxide, halide, sulfate, bisulfate, sulfonate, phosphate, phosphonate, perchlorate, nitrate, alkoxide (RO " , wherein R is a straight chain or branched alkyl group having 1 to 8 carbon atoms), phenoxide, carbonate (i.e. C0 3 " ), bicarbonate (i.e.
• alkonate (RC0 2 " , wherein R is a straight chain or branched alkyl having 1 -8 carbon atoms)
• the lithium salt is a lithium salt having the general formula Li n X, as described above, and may include the following structures:
• n is from 1 to 2
• the lithium salt is selected from the group consisting of lithium hydroxide, anhydrous lithium hydroxide, lithium methoxide, lithium carbonate, lithium chloride, lithium acetate, and lithium methacrylate, and combinations thereof.
• the lithium salt preferably comprises anhydrous lithium hydroxide.
• the amount of lithium salt used in the inventive process is from 0.1 to 10 mole%, or more preferably from 0.5 to 5 mole %, or most preferably from 1 to 2 mole%, based on the total moles of alkene- or polyene-containing alcohol in the reaction mixture.
• the lithium salt comprises one or more embodiments described herein.
• lithium salt catalysts such as those described herein, perform best when water is removed from the reactants prior to starting the transesterification reaction.
• Low levels of water sometimes found in the starting reactants, such as the alkene- or polyene-containing alcohols and for the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid can be removed, prior to the addition of the lithium salt by, for example, simple distillation of the reaction mixture until a small amount of the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is distilled overhead.
• less than 5% of the starting alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is removed by distillation from the alcohol/carboxylate mixture.
• distillation is carried out until water levels within the composition containing the alkene- or polyene-containing alcohol and the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is less than 0.10%, more preferably less than 0.05%, and most preferably less than 0.03% by weight based on the total weight of the solution including the alkene- or polyene-containing alcohol and alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid.
• the water level is most preferably less than 0.03% by weight based on the total weight of the solution including the alkene- or polyene-containing alcohol and alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid prior to adding the lithium salt.
• the alkene- or polyene-containing alcohol and alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid are reacted in the presence of at least two inhibitors.
• Inhibitors prevent the monomers of alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid present, including the asymmetrical polyene monomers formed by the inventive process, from polymerizing during transesterification and during storage. Inhibitors may also impact process stability for downstream applications.
• inhibitors include, and are not limited to, oxygen; diethylhydroxylamine; benzoquinone; hydroquinone (HQ); alkyl ethers of hydroquinone and derivatives thereof (including, for example, the methyl ether of hydroquinone (MeHQ) and derivatives thereof); phenothiazine; 2,3-dihydroxylnapthalene; dialkylpara-cresol (including, for example, 2,6-di-t-butylpara-cresol); dialkyl-4-hydroxyanisole (including, for example, 3,5-di-t- butyl-4-hydroxyanisole); dialkylhydroxyanisole (including, for example, 2,5-di-t- butylhydroxyanisole); trialkylphenol (including, for example, 2,4,6-tri-ter/-butylphenol); dialkyl- 6-alkylphenol (including, for example, 2,4-dimethyl-6-1 ⁇ 2r/-butylphenol (topanol A)); 4-hydroxy
• the alkyl group may be a substituted alkyl or unsubstituted alkyl group.
• the total amount of inhibitor used in the inventive process is at least 100 ppm to at most 3,500 ppm, or more preferably at most 2,500 ppm, or most preferably at most 2,000 ppm, based on the amount in weight of alkene- or polyene-containing alcohol.
• the total amount of inhibitor in the reaction mixture is from 200 to 2,500 ppm based on the amount in weight of alkene- or polyene-containing alcohol.
• a combination of at least two inhibitors is used.
• a combination of at least two inhibitors is used, wherein the first inhibitor is a hydroquinone- or phenol-type inhibitor (including, for example, hydroquinone, alkyl substituted phenol, or alkyl substituted hydroquinone) , and wherein the second inhibitor is an N-oxyl-containing compound.
• the first inhibitor is a hydroquinone- or phenol-type inhibitor (including, for example, hydroquinone, alkyl substituted phenol, or alkyl substituted hydroquinone)
• the second inhibitor is an N-oxyl-containing compound.
• a combination of at least two inhibitors is used, wherein the first inhibitor (component B) comprises a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl- substituted hydroquinone, a substituted alkyl-substituted hydroquinone, and combinations thereof, and wherein the second inhibitor (component C) comprises a piperidinyloxy radical-type inhibitor (including piperidinyloxy radicals with an alkyl- or hydroxyl- substitution on the cyclic ring structure).
• the first inhibitor comprises a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl- substituted hydroquinone, a substituted alkyl-substituted hydroquinone, and combinations thereof
• the second inhibitor (component C) comprises a piperid
• a combination of at least two inhibitors is used, wherein the first inhibitor (component B) comprises a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, an alkyl-substituted hydroquinone, and combinations thereof, and wherein the second inhibitor (component C) comprises a piperidinyloxy radical-type inhibitor (including piperidinyloxy radicals with an alkyl- or hydroxy]- substitution on the cyclic ring structure).
• the first inhibitor comprises a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, an alkyl-substituted hydroquinone, and combinations thereof
• the second inhibitor (component C) comprises a piperidinyloxy radical-type inhibitor (including piperidinyloxy radicals with an alkyl- or hydroxy]- substitution on the cyclic ring structure).
• component B has the general structure (IV)
• X is R or OR; R is CH 3 or H; and each R ⁇ R", R'" and R"" is, independently, H, a straight chain or branched alkyl group with 1 to 20 carbons, or an aromatic group, including aromatic groups comprising a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or share a common bond.
• component B is selected from the group consisting of MeHQ, derivatives of MeHQ, and HQ.
• component B is MeHQ or HQ, as shown in structures (V) and (VI), respectively, below.
• the concentration of component B is from 50 to 3,000 ppm, more preferably from 100 to 2,000 ppm, and most preferably from 250 to 1 ,500 ppm by weight based on the weight of asymmetrical polyene.
• the second inhibitor comprises an N-oxyl-containing compound (component C).
• component C N-oxyl-containing compound
• N-oxyl-containing compound refers to any compound and/or chemical substance containing the structural fragment
• component C is selected from the group consisting of 2,2,5, 5-tetramethyl-3-oxopyrrolidine-l -oxyl free radical; 2,2,6,6- tetramethylpiperidine-l-oxyl free radical; tris(2,2,6,6-tetramethylpiperidine-l -oxyl-4-yl)- phosphite; and4-hydroxy-2,2,6,6-tetramethylpiperidine- 1 -oxyl free radical (4-hydroxy TEMPO, or 4-HT); and derivatives of these compounds.
• the terms "4-hydroxy-2,2,6,6-tetramethylpiperidine-l -oxyl free radical" and "4-hydroxy-TEMPO" are synonymous and refer to a compound with the structure (VII)
• each R-R'" is, independently H or an alkyl. In one embodiment, each R-R'" is preferably CH 3 .
• component C is preferably selected from the group consisting of 4-hydroxy TEMPO and derivatives thereof.
• component C is preferably 4-hydroxy TEMPO.
• the concentration of component C (the N-oxyl-containing compound) used in the process described herein is less than that of component B.
• the concentration of component C is from 50 to 250 ppm, or more preferably from 75 to 125 ppm by weight based on the weight of asymmetrical polyene.
• the inventive process is a transesterification process to form a composition comprising an asymmetrical polyene which contains an " ⁇ , ⁇ unsaturated - carbonyl end" and a "C-C double bond end.”
• the asymmetrical polyenes resulting from the process described herein are useful as monomers in further polymerization reactions.
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is selected from the group consisting of the following:
• Ri is selected from H or a C
• R 2 is selected from H or a Ci-C 6 alkyl (preferably a C 1 -C3 alkyl and more preferably CH 3 );
• R 3 is selected from H, CH 3 , or CH 2 CH 3 ;
• ⁇ is selected from H, CH 3 , or CH 2 CH 3 ;
• n is from 1 to 50, or from 1 to 20, or further from 1 to 10;
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is a) as shown above.
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is selected from the group consisting of the following: b) and c), each as shown above, and in a further embodiment, b) wherein R 3 and R are both H; or when R 3 is CH 3 or CH 2 CH 3 , then R is H; or when R4 is CH 3 or CH 2 CH 3 , then R 3 is H.
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is b) as shown above.
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is b) as shown above, and in a further embodiment, b) wherein R 3 and R 4 are both H, or when R 3 is CH 3 or CH 2 CH 3 , and R 4 is H, or when R4 is CH 3 or CH 2 CH 3 , and R 3 is H.
• the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is c) as shown above.
• the "C-C double bond end" of the asymmetrical polyene is selected from the group consisting of the following:
• R5 is selected from H or C1 -C6 alkyl
• the - ⁇ TM ⁇ " ' notation represents a break at the center of a covalent bond between the "C-C double bond end" of the
• the "C-C double bond end" of the asymmetrical polyene is selected from the group consisting of the following: 1)-15) and 17), each as shown above.
• the "C-C double bond end" of the asymmetrical polyene is selected from the group consisting of the following: 1 ), 2), 3), 4), 5), 6), 7), 8), 9), 10), 1 1 ), 12), and 17), each as shown above.
• the "C-C double bond end" of the asymmetrical polyene is selected from the group consisting of the following: 1), 2), 3), 12), and 17) each as shown above.
• the "C-C double bond end" of the asymmetrical polyene is selected from the group consisting of the following: 13), 14), 15) and 16), each as shown above.
• the asymmetrical polyene is selected from the group consisting of the following:
• n is from 1 to 50, further from 1 to 20 and further from 1 to 10;
• R a is selected from H or an alkyl (preferably ethyl or methyl and more preferably methyl);
• R b is selected from H or an alkyl (preferably ethyl or methyl and more preferably methyl); and preferably wherein R a and R b are selected from the group consisting of (i) R a and R are both H, (ii) when R a is methyl, then R b is H, and (iii) when R a is H, then R b is meth l;
• the asymmetrical polyene is selected from the group consisting of the following: i), ii), iii), iv) and v), each as shown above.
• the asymmetrical polyene is selected from the group consisting of the following: i) and v), each as shown above.
• the asymmetrical polyene is selected from the group consisting of the following: vi), vii), and viii), each as shown above.
• the asymmetrical polyene is polypropylene glycol allyl ether methacrylate (PPG AEMA) having the structure
• n is from 1 to 50, further from 1 to 20 and further from 1 to 10;
• R a is selected from H or an alkyl (preferably ethyl or methyl and more preferably methyl);
• R b is selected from H or an alkyl (preferably ethyl or methyl and more preferably methyl); and preferably wherein R a and R b are selected from the group consisting of (i) R a and R b are both H, (ii) when R a is methyl, then R b is H, and (iii) when R a is H, then R b is methyl.
• Asymmetrical Polyene Composition [0081]
• the present invention provides a composition comprising the asymmetrical polyene composition.
• the composition may include an asymmetrical polyene, inhibitors, and lithium salt.
• the total amount of inhibitor and/or derivative(s) thereof present in the asymmetrical polyene composition is from 75 to 3,500 ppm.
• the amount of first inhibitor and/or derivative(s) thereof (component B) present in the asymmetrical polyene composition is from 50 to 3000 ppm based on the weight of the composition
• the amount of the second inhibitor and/or derivative(s) thereof (component C) present in the asymmetrical polyene composition is from 25 to 500 ppm based on the weight of the composition.
• the asymmetrical polyene composition includes an asymmetrical polyene and, preferably, less than 100 ppm of the second inhibitor (component C), which is an N-oxyl-containing compound and/or derivative(s) thereof, wherein the ppm is based on the weight of the asymmetrical polyene.
• the asymmetrical polyene composition includes an asymmetrical polyene and, preferably, from 500 ppm to 1500 ppm of the first inhibitor (component B), and 75 ppm of the second inhibitor (component C), wherein the ppm is based on the weight of the asymmetrical polyene.
• the amount of first and second inhibitor (components B and C) present in the asymmetrical polyene composition is determined by mass balance equation.
• the asymmetrical polyene composition comprise less than 100 ppm of an inhibitor selected from the group consisting of 4-HT, and/or derivatives thereof, and less than 2000 ppm MeHQ and/or derivatives thereof, each based on the weight of the composition.
• the amount of 4-HT and/or its derivatives in ppm is determined from a mass balance equation.
• the amount of MeHQ and/or derivatives thereof in ppm is determined using HPLC or GC.
• the composition comprises unreacted alkene- or polyene- containing alcohol and/or unreacted alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in addition to asymmetrical polyene, inhibitors, and lithium salt.
• the composition comprises from 2% to 10 %, or from 2% to 8%, or from 2% to 6%, or from 2% to 4%, by weight, of unreacted alkene- or polyene-containing alcohol, based on the total weight of the composition.
• the composition comprises less than 10%, or less than 8%, or less than 6%, or less than 2%, by weight, of unreacted alkene- or polyene-containing alcohol, based on the total weight of the composition.
• the composition may include by-products, such as Michael adducts.
• the composition comprises from 2% to 10 %, or from 2% to 8%, or from 2% to 6%, or from 2% to 4%, by weight, of Michael adducts based on the total weight of the composition.
• the composition comprises less than 10%, or less than 8%, or less than 6%, or less than 4%, by weight, of Michael adducts, based on the total weight of the composition.
• the invention includes an asymmetrical polyene made an inventive process described herein.
• the asymmetrical polyene or asymmetrical polyene composition may be used to form a polymer.
• the polymer is an ethylene-based polymer.
• the polymer is low density polyethylene (LDPE).
• the polymer made using the asymmetrical polyene composition, and polymer blends, and/or compositions including the asymmetrical polyene, may be used to form an article or at least one component of an article.
• the polymer made using the asymmetrical polyene composition, and polymer blends, and/or composition including the asymmetrical polyene may be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including extrusion coating onto various substrates; monolayer and multilayer films; molded articles, such as blow molded, injection molded, or rotomolded articles; coatings; fibers; and woven or non- woven fabrics.
• a polymer made using the symmetrical polyene composition, and polymer blends, and/or compositions including the asymmetrical polyene may be used in a variety of films, including but not limited to, clarity shrink films, collation shrink films, cast stretch films, silage films, stretch hood, sealants, and diaper backsheets.
• the present invention is a transesterification process to form a composition comprising an asymmetrical polyene which contains an " ⁇ , ⁇ unsaturated - carbonyl end" and a "C-C double bond end," the process comprising reacting an alkene- or polyene- containing alcohol with an alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in the presence of at least the following components: A) a lithium salt; B) a hydroquinone, alkyl-substituted phenol, or alkyl-substituted hydroquinone; and C) an N-oxyl-containing compound to form a solution comprising the asymmetrical polyene, and wherein the " ⁇ , ⁇ unsaturated - carbonyl end" of the asymmetrical polyene is selected from the group consisting of structure a)-c), as described herein, and the "C-C double bond end" of the asymmetrical polyene is selected
• the alkene- or polyene-containing alcohol, the ⁇ , ⁇ unsaturated carboxylic ester, lithium salt (component A) and inhibitors (components B and C) may be added to the reaction in any order.
• the alkene- or polyene-containing alcohol, the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid and the inhibitors (components B and C) are first combined, followed by addition of the lithium salt (component A).
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid and inhibitors (components B and C) are first combined, followed by the addition of the alkene- or polyene-containing alcohol, and, separately, the lithium salt (component A).
• the alkene- or polyene-containing alcohol, the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid and the inhibitors (components B and C) are first combined, and the resulting mixture is heated to distill a small amount of the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid overhead to help remove low levels of water which may be present in the raw materials (i.e., alkene- or polyene-containing alcohol, alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid and inhibitors).
• the lithium salt (component A) is added to the reaction.
• the reaction mixture is heated to above 60°C, and preferably to a reaction temperature which ranges from 70°C tol40°C, for transesterification to occur.
• the reaction temperature is preferably from 70°C to 125°C, more preferably from 80°C to 120°C, or most preferably from 85°C to 100°C.
• the reaction pressure is typically from 760 mmHg to reduced pressures.
• the reaction pressure is from 250 to 760 mmHg, or more preferably from 400 to 760 mmHg.
• the reaction time is typically from 3 to 48 hours, and preferably from 5 to 18 hours, and most preferably 6 to 12 hours.
• the reactor overhead can possess either a packed or trayed distillation column or other means to help establish an azeotrope between the alkyl ester of an a, ⁇ unsaturated carboxylic acid [e.g. (meth)acrylate ester] and the alcohol of reaction, or alcohol2, which is the corresponding alcohol from the ester portion of the alky] ester of an ⁇ , ⁇ unsaturated carboxylic acid (for example, methanol would be formed from transesterification reactions involving methyl methacrylate).
• the azeotrope typically is composed of a higher concentration of the alcohol2 over the (meth)acrylate. In this way, the by-product alcohol2 can be removed with minimum loss of the (meth)acrylate raw material.
• the process of the present invention includes removing excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid.
• the step of removing excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises cooling the asymmetrical polyene solution and distilling the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid. In one embodiment, the solution is cooled to below 50°C.
• the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid is distilled using a straight lead distillation tower.
• the distillation rate is maintained such that distillation is complete in 1 to 4 hours, or preferably 1 to 3 hours, or more preferably 1 to 3 hours, or most preferably 1 to 20 hours.
• the step of removing excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid comprises cooling the asymmetrical polyene solution, preferably to below 50°C, and applying a vacuum to bring the pressure down to less than or equal to 200 mmHg prior to distilling the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid.
• the solution is heated to a temperature of greater than or equal to 70°C after attaining a pressure of less than or equal to 200 mmHg and prior to distilling the alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid.
• the pressure is decreased during distillation while the temperature is increased.
• the pressure is decreased over about 1 hour to 30 mmHg and the temperature is increases during that 1 hour to 88°C to 92°C, or preferably 90°C. If possible, the pressure may be further decreased over an additional 15 to 30 minutes while the temperature is maintained at 88°C to 92°C, or preferably 90°C.
• excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid removal is complete when no more alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid appears overhead after the asymmetrical polyene solution reaches a pressure of less than or equal to 30 mmHg and a temperature of 90°C. In one embodiment, excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid removal is complete when the amount of alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid in the asymmetrical polyene solution is less than or equal to 0.5 weight percent, or preferably less than 0.5 weight percent, as measured by chromatography.
• excess alkyl ester of an ⁇ , ⁇ unsaturated carboxylic acid removed is recycled and used in further reaction with alkene- or polyene-containing alcohol to form additional asymmetrical polyene, as described herein.
• the process of the present invention includes filtering the asymmetrical polyene solution. Filtering the asymmetrical polyene solution may remove lithium salt (component A) present in the solution.
• the process includes filtering the asymmetrical polyene solution using a 10 micron or less filter, or a 5 micron or less filter, or a 2 micron or less filter, or a 1 micron or less filter.
• the process of the present invention includes cooling the asymmetrical polyene solution.
• the process includes cooling the asymmetrical polyene solution to a temperature of less than or equal to 5°C, or less than or equal to 4°C, or less than or equal to 3°C, or preferably, less than or equal to 2°C.
• the transesterification process of the present invention comprises filtering the asymmetrical polyene solution at a temperature of less than or equal to 5°C, using a 10 micron or less filter, or a 5 micron or less filter, or a 2 micron or less filter, or a 1 micron or less filter.
• the temperature of the asymmetrical polyene solution is decreased to less than or equal to 5°C, to cause the lithium salt to precipitate out of solution before filtration.
• the asymmetrical polyene solution is filtered at a temperature of less than or equal to 5°C, or less than or equal to 4°C, or less than or equal to 3°C, or preferably, less than or equal to 2°C, or preferably less than 0°C, using a 10 micron or less filter, or a 5 micron or less filter, or a 2 micron or less filter, or a 1 micron or less filter.
• the asymmetrical polyene solution is filtered at a temperature of less than or equal to 5°C, or less than or equal to 4°C, or less than or equal to 3°C, or preferably, less than or equal to 2°C.
• the asymmetrical polyene solution is filtered at a temperature of less than or equal to 0°C.
• the asymmetrical polyene solution may be held at the temperature of less than or equal to 5°C, for a period of at least 1 hour, or more preferably at least 2 hours, or most preferably at least 3 hours to allow the lithium salt to precipitate prior to filtering.
• filtering the asymmetrical polyene solution at a temperature of less than or equal to 5°C, using 1 micron or smaller filter also results in an asymmetrical polyene solution, which, upon standing at ambient temperature for up to 24 hours after filtration, or up to 72 hours after filtration, or up to 60 days after filtration, or up to 180 days after filtration showed little to no haze.
• alkyl refers to a saturated linear, cyclic, or branched hydrocarbon group.
• suitable alkyl groups include, for example, methyl, ethyl, n-propyl, i -propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc.
• the alkyls have 1 to 20 carbon atoms.
• substituted alkyl refers to an alkyl as previously described in which one or more hydrogen atom bound to any carbon of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, 2-propenyl (or allyl), vinyl, haloalkyl, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, unsaturated hydrocarbon, and combinations thereof.
• Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
• composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
• polymer refers to a compound prepared by polymerizing monomers, whether of the same or a different type.
• the generic term polymer thus embraces the term homopolymer (which refers to polymers prepared from only one type of monomer with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer” as defined below. Trace amounts of impurities may be incorporated into and/or within the polymer.
• interpolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
• the generic term interpolymer includes copolymers (which refers to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
• blend refers to a mixture of two or more components.
• polyene refers to a poly-unsaturated compound having two or more carbon-carbon double bonds.
• ethylene-based polymer refers to a polymer that comprises a majority amount of polymerized ethylene, based on the weight of the polymer, and, optionally, at least one comonomer.
• Rl As used herein, the terms “Rl ,” R2,” and the like, are used interchangeably with “Ri,” “R 2 “ and the like to refer to corresponding R groups forming part of a chemical structure. Similarly, the terms “CI ,” “C2,” and the like, are used interchangeably with “Ci,” “C 2 “ and the like to refer to 1- or 2-carbon groups, respectively.
• Polymer observation during/after reaction Polymer observation is determined both by direct observation of reaction and product samples, and also via solvent dilution tests, followed by visual confirmation for lack of haze, solids, gels, coagulum, stringy material, etc.
• solvent dilution tests samples are tested using both methanol and hexane.
• the reaction mixture is evaluated at various stages, by mixing 1 gram of reaction mixture or final product with 49 grams of anhydrous methanol, for the methanol dilution test, or 49 grams of hexane, for the hexane dilution test.
• Significant haze development upon dilution, after 5 minutes, using either dilution test indicates formed polymer and a failed test.
• Extended storage stability tests are run directly, by placing the monomer at 54°C, and the monomer samples need to last 60 days, without evidence of polymer formation via these test methods. This would qualify the monomer for acceptable storage times during commercial use.
• Mass balance is employed for the determination of inhibitor concentration.
• Inhibitor concentrations may also be determined by HPLC methods, as well as other methods known in the art.
• Reaction preparation A four-necked, 2-liter flask is equipped with a mechanical stirrer, a sparge tube for 8% oxygen in nitrogen gas feed, and a 10-15 sieve-tray distillation column (or packed column), with a condenser on top leading distillate, to a reflux splitter that controls the amount of distillate going forward to a receiver, versus back to the column as reflux; where the receiver leads to a vacuum source that is controlled by a pressure transducer.
• Thermocouples are placed, within the reactor flask and in the overhead space above the column, to help monitor and control temperatures at these locations.
• the reaction flask is charged with 400 grams of polypropyleneglycol mono-allyl ether (2 moles), 1000 grams of methyl methacrylate (MMA) (10 moles), and 0.8 grams of the methyl ether of hydroquinone (MeHQ) and then sealed.
• MMA methyl methacrylate
• MeHQ hydroquinone
• 0.04 grams of 4-hydroxy-TEMPO (4H-TEMPO) is also added.
• 0.2 grams of MeHQ are added to the overhead receiver to inhibit MMA monomer that will collect there.
• Chilled water (10°C) is fed to the coolant side of the overhead condenser.
• the mechanical agitator is turned on and set to 100 rpm.
• the 8% oxygen in the nitrogen sparge flow is started and maintained at a flow rate of approximately 10 mis/minute.
• This temperature drop in the overhead results from the establishment of an MMA/methanol azeotrope that forms, which is important to maintain during the course of the reaction for faster methanol removal with minimum MMA loss.
• the distillate is taken forward at a rate of 2.3: 1 reflux:distillate ratio.
• the overhead should then be set to full reflux mode, until the overhead temperature comes back down into the 56- 58°C range. Once this is accomplished, the overhead can be reset to the 2.3 : 1 reflux ratio once more.
• the time for this step is approximately 4 to 8 hours, and can be monitored either by measuring the amount of methanol formed in the distillate, or by measuring conversion of the starting alcohol to the corresponding methacrylate ester in the pot using either GC or NMR analysis. Once the analytical confirms that the conversion of the starting alcohol to the ester product is over 97%, the batch will then be stripped of excess MMA.
• the pressure is decreased, over about one hour, to 30 mmHg, while also increasing temperature over this time to 90°C. If possible to lower the pressure further, this should be accomplished over an additional 15 to 30 minutes, while maintaining a batch temperature of 88°C to 92°C.
• a sample is withdrawn from the reaction mixture to measure for residual MMA by chromatography. Once the MMA is below 0.5 weight%, the vacuum is broken with air, and the batch is cooled to ambient temperature. If the MMA level is above 0.5 weight%, then the batch is further held at less than 30 mmHg and also 90°C, for another hour, before checking the MMA level again.
• Table 1 illustrates the beneficial effect of certain inhibitors on conversion versus time, and also on reaction and product stability.
• the inhibitor amounts listed in Table 1 are based on the starting mixture once all charges of all raw materials are made. Polymer observation is conducted using both methanol and hexane dilution tests.
• MeHQ methyl ether of hydroquinone
• the 2 nd shot of LiOH is equal to 1 ⁇ 4 of the original amount of LiOH added to the batch.
• Examples 6 to 1 1 are prepared as described according to the general procedure above, except that 0.8 grams of the methyl ether of hydroquinone (MeHQ) and 0.04 grams of 4- hydroxy-TEMPO (4H-TEMPO) are employed as inhibitors for each of examples 6 to 1 1 and different precipitation and filtration temperatures are used as outlined in Table 2.
• MeHQ hydroquinone
• 4H-TEMPO 4- hydroxy-TEMPO
• Table 2 shows the beneficial effect of lower temperatures on lithium salt removal.
• Table 2 Effect of Precipitation/Filtration Temperature on Lithium Salt Removal
• LDPE low density polyethylene
• melt strength is still desired. It has been discovered that such polymers can be produced using asymmetrical polyenes, such as those described herein. However, there is a need to produce such polymers under polymerization conditions with good reactor stability.
• the propensity for each compound to shift the baseline level of radicals in the process must be considered.
• a given compound may generate radicals independent of other materials injected into the reactor.
• an interaction between two compounds may generate additional radicals.
• Table 3 shows the corresponding amount of DTBP and 4-HT used for the experiment, as well as the amount of active oxygen due to peroxides in the base alcohol (the alcohol used to produce the PPGAEM).
• the amount of 4-HT in ethylene was based on the weight fraction of 4- HT in the PPGAEM determined from the mass balance when producing the PPGAEM.
• the temperature of the reactor 30 seconds after injection of the reaction components (T@ 30s) was recorded, and the results are included for each experiment.
• Experiments 12 to 15 illustrate that T@ 30s rises as the amount of 4-HT is increased when using the same amount of DTBP.
• Experiment 16 and Experiment 17 illustrate at the same concentration of DTBP, the T@ 30s was lower for the experiment with the PPGAEM produced from the base alcohol which had a much lower amount of active oxygen due to peroxides.
• Examples 16 to 20 illustrate it was possible to use higher amounts of DTBP for the experiments with the PPGAEM produced from the base alcohol, which had a much lower amount of active oxygen due to peroxides.
• Experiments 12 to 20 illustrate an improved capability to avoid reactive runaway decomposition reactions through a higher degree of control over radicals or compounds, which can initiate polymerization of ethylene in the high pressure low density polymerization process, when minimizing the 4-HT and the peroxides in the base alcohol used to produce the PPGAEM.

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